Transalkylation of alkylated phenols

ABSTRACT

Transalkylation processes using catalysts comprising three dimensional 12 membered ring zeolites with a combination of small and large pores are described. These catalysts have increased conversion of alkylphenols to phenol, cresols, and alkylbenzenes from coal-derived liquid streams compared to catalysts consisting of HZSM-5 zeolite.

BACKGROUND OF THE INVENTION

Low and medium temperature coal tar contains an abundant of valuableoxygenate compounds such as phenol, cresols, and xylenols along withless desirable longer-chain alkylphenols in the feed.

Direct dealkylation can be employed to convert the alkylphenols;however, there are a number of problems associated with the process.When direct dealkylation is done without a catalyst, the processtemperature is in the range of 700 to 900° C. This can lead to thedealkylation of the phenols through thermal cracking at the high processtemperature. It is quite energy intensive because of the high processtemperature. In addition, it is normally not selective due to the lossof the hydroxyl group. Catalytic dealkylation can be done at much milderconditions. At temperatures from 300 to 400° C., ethylphenol andpropylphenol can be dealkylated to produce phenol and ethylene/propyleneon a ZSM-5 zeolite. However, water usually has to be co-fed to preventsevere catalyst deactivation. In addition, cresols dealkylation isrelatively difficult, and phenol selectivity can be a concern.

Therefore, there is a need for improved methods of convertingalkylphenols in coal tar feeds to obtain phenol and xylenes.Transalkylation of the alkylphenols with a co-reactant (e.g., aco-reactant such as benzene or toluene) can help to prevent the loss ofthe hydroxyl group due to less severe process temperatures and willproduce alkylbenzenes as co-products which are more valuable compared toethylene/propylene produced from dealkylation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a comparison of the conversion of 4-ethylphenol in atransalkylation process using a variety of catalysts comprisingzeolites.

FIG. 2 illustrates a comparison of the conversion of 2,6-xylenols in atransalkylation process using a variety of catalysts comprisingzeolites.

FIG. 3 illustrates a comparison of the conversion of 4-ethylphenol in atransalkylation process with N₂ and H₂ co-feed using HZSM-5 SAR 80 andHBeta SAR 25 zeolites.

FIG. 4 illustrates a comparison of the conversion of (A) ethylphenolsand (B) xylenols from a cresylic acid feed in a transalkylation processusing a variety of catalysts comprising zeolites.

FIG. 5 illustrates a comparison of the conversion of (A) ethylphenolsand (B) xylenols from a cresylic acid feed in a transalkylation processusing HBeta SAR 25 compared to HBeta SAR 25 (80%) mixed with otherzeolites (20%).

DESCRIPTION OF THE INVENTION

Coal-derived feed streams, such as low temperature coal tar, mediumtemperature coal tar, high temperature coal tar, cresylic acid, or acrude phenolic mixture contain phenol, alkylphenols (methylphenols(cresols), ethylphenols, dimethylphenols(xylenols), propylphenols,butylphenols, methylethylphenols, etc.), as well as heavier alkylphenols(such as indanols and napthols). Coal tar is derived from the process ofdry distillation and gasification of coal and is classified based on thetemperature used for this process (400-600° C. (low temperature),600-1000° C. (medium temperature), and >1000° C. (high temperature)).Cresylic acid is a generic term referring to combinations of phenol andalkylphenols, and it can be obtained from either coal or petroleumprocessing, for example. A crude phenolic mixture can be obtained by theprocessing of coal tar oils and the purification of phenol containingwaste from coke ovens, low temperature carbonization, and hydrogenationplants, for example. The composition of the feed stream will varydepending on its source.

The undesirable longer-chain alkylphenols in the coal-derived feedstreams can be separated into a coal-derived liquid stream and convertedto valuable products including, but not limited to, phenol, cresols, andxylenes by transalkylation. The alkylphenols in the coal-derived liquidstream can be transalkylated with a co-reactant (e.g., a co-reactant,such as benzene and/or toluene) to transfer the longer-chain alkyl group(for example, ethyl, propyl, butyl, etc.) to obtain phenol andalkylbenzenes as the new products. The alkylbenzenes, for example,xylenes, ethylbenzene, and ethyltoluenes, are in demand for industrialprocesses and have higher value compared to toluene. In some cases, ithas been determined that phenols with methyl groups, such as cresols,xylenols, and trimethylphenols, are not easily transalkylated with anaromatic compound so the valuable phenolics remain intact.

WO 2019177458 (WO ′458) demonstrated that 4-propylphenol (model feed forbiomass lignin-derived phenol) can be transalkylated with benzene usingan HZSM-5 catalyst. Several other zeolites were tested (HMOR and HY) butwere not as active as HZSM-5.

In “Conversion of alkylphenol to phenol via transalkylation usingzeolite catalysts,” Yoshikawa et al., Catalysis Today, (2018),https://dol.org/1-.1016/j.cattod.2-18.08.009, it was demonstrated that4-propylphenol (a model feed for biomass lignin-derived phenol) can betransalkylated with benzene in a batch reactor over HBeta, HZSM-5 andHMOR zeolites. They found that HZSM-5 yielded a greater amount oftransalkylation products (phenol and propylbenzenes) than HBeta or HMORzeolites.

US 2020/0031741 describes a process and apparatus for cresoltransalkylation with toluene and/or benzene to phenol andaromatics/alkylbenzenes in the presence of transalkylation catalysts(homogeneous or heterogeneous acid catalysts) from coal-derived liquids.It also describes xylenol transalkylation with benzene to make phenoland aromatics/alkylbenzenes in the presence of transalkylationcatalysts.

However, the feeds in these references were limited (i.e., a singlecompound) and did not involve a broad range of alkylphenols. Low andmedium temperature coal tar, cresylic acid, and a crude phenolic mixtureare complex mixtures of alkylphenols, and contain a greater percentageof dimethylphenols (e.g., 3.0-34.5 wt %), methylethylphenols (e.g.,0-3.0 wt %) and ethylphenols (e.g., 2.0-38.5 wt %) than propylphenols(e.g., 0-1%). The methyl and ethyl groups of alkylphenols are muchharder to remove than the propyl groups.

The coal-derived liquid stream from the coal-derived feed streamcomprises a complex mixture of alkylphenols comprising one or moremethylphenols (cresols), ethylphenols, dimethylphenols (xylenols),propylphenols, butylphenols, methylethylphenols, etc.), as well asheavier alkylphenols (such as indanols and napthols). It has been foundthat catalysts comprising three dimensional 12 membered ring zeoliteswith a combination of smaller and larger pores have increased conversionof these complex mixtures of alkylphenols to phenol, cresols, andalkylbenzenes compared to catalysts consisting of HZSM-5 zeolite.

One suitable zeolite comprising three dimensional 12 membered rings witha combination of smaller and larger pores is HBeta zeolite. Catalystsmade with these zeolites have increased conversion of complex mixturesof alkylphenols as described above to phenol, cresols, and alkylbenzenescompared to catalysts consisting of HZSM-5 zeolite. The catalystscomprising HBeta zeolites are very stable in the transalkylationprocess, with less than about 5% decrease in conversion of alkylphenolsto phenol, cresols, and alkylbenzenes over 25 hr. As a result, catalystscontaining HBeta zeolites can be successfully used to convert low andmedium temperature coal tar, cresylic acid, or a crude phenolic mixtureto phenol, cresols, and aromatics, such as benzene and xylenes.

Any suitable HBeta zeolite can be used. HBeta zeolite is a threedimensional zeolite with 12 membered ring channels and a combination oflarge and small pores. The diameter of the larger pores are 6.6×6.7(Å),and the diameter of the small pores are 5.6×5.6 (Å)(www.iza-structure.org/databases/). The aluminum in the zeoliteframework structure may be substituted, either partially or completely,by other metals including, but not limited to, Fe, Ga, B, Ti, Sn, Zr,and combinations thereof. The HBeta zeolite can have a silica/metaloxide molar ratio of 1-200, or 200 or below, or 150 or below, or 100 orbelow, or 80 or below, or 60 or below, or 50 or below, or 40 or below,or 30 or below, or 25 or below. When the metal oxide is alumina, this iscommonly referred to as SAR (silica/alumina (SiO₂/Al₂O₃) ratio). Whenanother metal is partially substituted for aluminum in the frameworkstructure, the amount of metal oxide in the silica/metal oxide ratio isthe total amount of metal oxide (i.e., the amount of alumina+the amountof other metal oxide). HBeta zeolites are available from many companies,including, but not limited to, Zeolyst International, Clariant Ltd, andTOSOH Corporation. Some properties of HBeta zeolites are compared toother common zeolites in Table 1.

Of the HBeta zeolites tested, the catalysts containing HBeta SAR 25zeolites were found to be the best catalysts for transalkylation ofethylphenols and methylphenols with toluene and for the transalkylationof 2,6 xylenol with toluene.

The catalyst comprising HBeta zeolite has a product selectivity tophenol, cresols and alkylbenzenes is 70% or more, or 75% or more, or 80%or more, or 85% or more, or 90% or more, or 95% or more. The catalystcomprising HBeta zeolite has a conversion of 4-ethylphenol of 60% ormore, or 65% or more, or 70% or more, or 75% or more, or 80% or more.The catalyst comprising HBeta zeolite has a conversion of 2,6-xylenol of20% or more, or 30% or more, or 40% or more.

The catalyst comprising HBeta zeolite has a productivity to phenol,cresols, and alkylbenzenes of 500 g/Kg-catalyst/h or more, or 750g/Kg-catalyst/h or more, or 1000 g/Kg-catalyst/h or more, or 1250g/Kg-catalyst/h or more, or 1300 g/Kg-catalyst/h or more, or 1500g/Kg-catalyst/h or more, or 1750 g/Kg-catalyst/h or more, or 2000g/Kg-catalyst/h or more.

${{{Conversion}(\%)} = {\frac{( {{{Reactant}{Moles}{IN}} - {{Reactant}{Moles}{OUT}}} )}{( {{Reactant}{Moles}{IN}} )} \times 100}}{{{Product}{Selectivity}( {{mol}\%} )} = {\frac{{Product}({moles})}{{All}{Carbon}{containing}{Products}({moles})} \times 100}}{{{Productivity}( \frac{g}{{kg} \cdot {hr}} )} = \frac{{Product}{Mass}{OUT}( \frac{g}{hr} )}{{Catalyst}{Amount}({kg})}}$

The catalyst composition can be modified to improve catalyst stabilityand selectivity to the desired products with minimal side reactions. Forexample, other zeolites (including, but not limited to, HZSM-5, HY,HMOR, HMCM-22, and others) can be mixed with HBeta to adjust theactivity and product selectivity. Additionally, the catalyst compositioncould include promoters typically including, but not limited to, one ormore of transition metals from Group IB to VIII, alkali metals fromGroup IA, alkaline earth metals from Group IIA, rare earth metals fromLanthanide series, metal oxides, metal sulfides, metal nitrides, metalphosphides, and combinations thereof. The catalyst can also be combinedwith a porous inorganic support material, such as alumina, silica,zirconia, titania, and combinations thereof.

The catalyst typically comprises about 50 wt % HBeta zeolite or more, orabout 60 wt % or more, or about 70 wt % or more, or about 75 wt % ormore, or about 80 wt % or more, or about 85 wt % or more, or about 90 wt% or more, or about 95 wt % or more, or about 50% to 100%, or about 50%to about 99%, or about 50% to about 97%, or about 50% to about 95%.

The catalyst may comprise less than about 40 wt % HZSM-5 catalyst, orless than about 35 wt %, or less than about 30 wt %, or less than about25 wt %, or less than about 20 wt %, or less than about 15 wt %, or lessthan about 10 wt %, or less than about 5 wt %, or less than about 3 wt%, or less than about 1 wt %.

The catalyst can perform transalkylation of alkylphenols includingmethylphenols (cresols), ethylphenols, dimethylphenols (xylenols),propylphenols, butylphenols, methylethylphenols, and the like, includingcomplex mixtures thereof, such as coal-derived liquid streams,efficiently and in a low-cost process.

The transalkylation process can be performed in any suitable reactortype, including but not limited to, fixed bed reactors, moving bedreactors, ebullated bed reactors, fluidized bed reactors, continuouscatalyst regeneration (CCR) reactors, semi-regenerative reactors, batchreactors, continuous stirred tank (CSTR) reactors, and slurry bedreactors, or combinations thereof.

Any suitable transalkylation reaction conditions can be used. Thetransalkylation reaction conditions will depend on the particularreactor type use, as is known in the art. For example, with a fixed bedreactor, the transalkylation reaction conditions can include at leastone of: a temperature in a range of about 50° C. to about 600° C.; apressure in a range of about 0 to about 15 MPa; or a liquid weighthourly space velocity in a range of about 0.1 to about 30 hr⁻¹. Those ofskill in the art can select the appropriate reaction conditions for thereactor being used.

One aspect of the invention is a process for transalkylation. In oneembodiment, the process comprises: transalkylating a coal-derived liquidstream comprising alkylphenols in a transalkylation reaction zone undertransalkylation conditions in the presence of a co-reactant and atransalkylation catalyst comprising a three dimensional 12 membered ringzeolite with a combination of small and large pores to produce atransalkylation effluent stream comprising one or more of phenol,cresols, and alkylbenzenes, the process having increased conversion ofalkylphenols to phenol, cresols, and alkylbenzenes compared to acatalyst consisting of HZSM-5 zeolite.

In some embodiments, the zeolite comprises about 50 wt % HBeta or more.

In some embodiments, the silica/metal oxide molar ratio of the zeoliteis 80 or below.

In some embodiments, the transalkylation catalyst further comprisesabout 40 wt % HZSM-5 zeolite or less.

In some embodiments, the transalkylation catalyst comprises about 50% ormore HBeta zeolite and 1 to 40% HZSM-5 zeolite, and wherein the processhas increased productivity to phenol or cresols or both compared to atransalkylation catalyst consisting of HZSM-5 zeolite.

In some embodiments, aluminum from the zeolite framework structure issubstituted by at least one of Fe, Ga, B, Ti, Sn, Zr, and combinationsthereof.

In some embodiments, the zeolite further comprises a promoter comprisingone or more of: transition metals, alkali metals, alkaline earth metalsand rare earth metals, metal oxides, metal sulfides, metal nitrides,metal phosphides, and combinations thereof.

In some embodiments, the catalyst further comprises a support comprisingalumina, silica, zirconia, titania, or combinations thereof.

In some embodiments, the coal-derived liquid stream comprises a mixtureof alkylphenols comprising two or more of: a methylphenol, anethylphenol, a dimethylphenol, a butylphenol, a methylethylphenol, anindanol, and a naphthol, and optionally further comprising apropylphenol.

In some embodiments, the co-reactant may be a co-reactant such asbenzene, toluene, or a combination thereof.

In some embodiments, transalkylating the coal-derived liquid streamtakes place in the presence of hydrogen, nitrogen, or a combinationthereof.

In some embodiments, the transalkylation reaction zone comprises a fixedbed reactor, a moving bed reactor, an ebullated bed reactor, a fluidizedbed reactor, a continuous catalyst regeneration (CCR) reactor, asemi-regenerative reactor, a batch reactor, a continuous stirred tank(CSTR) reactor, a slurry reactor, or combinations thereof.

In some embodiments, productivity to phenol, cresols and alkylbenzenesis 1300 g/Kg-catalyst/h or more.

In some embodiments, selectivity to phenol, cresols and alkylbenzenes isabout 70% or more.

In some embodiments, the coal-derived liquid stream comprises a lowtemperature coal tar stream, a medium temperature coal tar stream, ahigh temperature coal tar stream, a cresylic acid stream, or a crudephenolic mixture.

In some embodiments, the process further comprises: separating thetransalkylation effluent into a phenol product stream comprising thephenol and an alkylbenzene stream comprising the alkylbenzenes.

In some embodiments, the process further comprises: separating thealkylbenzene stream into at least a recycle co-reactant stream such asone or more of benzene or toluene; and recycling the recycle co-reactantstream to the transalkylation zone and wherein the recycle streamcomprises at least a part of the co-reactant.

In some embodiments, separating the alkylbenzene stream into at leastthe recycle co-reactant stream comprises separating the alkylbenzenestream into at least the recycle co-reactant stream and a mixed xylenesstream comprising para-xylene, ortho-xylene, and meta-xylene; andrecovering one or more of para-xylene, ortho-xylene, or meta-xylene fromthe mixed xylenes stream.

In some embodiments, separating the transalkylation effluent into theproduct stream and the alkylbenzene stream comprises separating thetransalkylation effluent into the phenol product stream, thealkylbenzene stream, and a cresol product stream comprising the cresols,and further comprises: recovering the cresol product stream.

In some embodiments, the transalkylation effluent stream furthercomprises unreacted alkylphenols, and wherein separating thetransalkylation effluent into the product stream and the alkylbenzenestream comprises separating the transalkylation effluent into the phenolproduct stream, the alkylbenzene stream, and an unreacted alkylphenolstream comprising the unreacted alkylphenols, and further comprises:recycling the unreacted alkylphenol stream to the transalkylationreaction zone.

In some embodiments, the process further comprises: providing acoal-derived feed stream comprising phenol and the coal-derived liquidstream; separating the coal-derived feed stream into at least a phenolstream comprising phenol and the coal-derived liquid stream beforetransalkylating the coal-derived liquid stream; and recovering thephenol stream.

In some embodiments, the process further comprises: providing acoal-derived feed stream comprising phenol and the coal-derived liquidstream; separating the coal-derived feed stream into at least aphenol-cresol stream comprising phenol and cresols and the coal-derivedliquid stream before transalkylating the coal-derived liquid stream; andrecovering the phenol-cresol stream.

EXAMPLES

The following commercial catalysts were evaluated.

Manufacture Silica/Alumina Molar Zeolite (Material Code) Ratio (SAR)*HBeta Clariant (HCZB25) 25 HBeta Zeolyst (CP814C) 38 HBeta Clariant(HCZB150) 150 HZSM-5 Clariant (NH4CZP30) 30 HZSM-5 Zeolyst (CBV8014) 80HZSM-5 Zeolyst (CBV28014) 280 HY Zeolyst (CBV500) 5.2 HY Zeolyst(CBV712) 12 HMOR Zeolyst (CBV21A) 38 *Provided by manufacturer.

Example 1

Several commercial zeolites were evaluated for the transalkylation of4-ethylphenol (4-EP) with toluene to form phenol and ethyltoluenes.

The reaction conditions included using an isothermal fixed bed reactorset to a temperature of 400° C., a pressure of 1350 psig, a WHSV of 2.3h⁻¹, 1.25 g catalyst, toluene:feed of 11 mol/mol, and N₂ feed rate of 25mL/min. The catalyst was pretreated in N₂ and heated to 200° C. (3°C./min) and held at 200° C. for 2 h followed by heating to 450° C. (5°C./min) and held for 3 h before cooling down to 400° C.

Table 2 and FIG. 1 show the results of the conversion of 4-ethylphenol.Conversion and selectivity were obtained after 30 h TOS (time on stream)for most runs. or 35 h TOS for HBeta SAR 25, HBeta SAR 150, and HZSM-5SAR 80. The product selectivity is based on the carbon productcomposition excluding toluene and 4-ethylphenol. BEX refers to benzene,ethylbenzene, and xylenes.

As shown in FIG. 1 , the catalysts comprising HBeta SAR 25 and HBeta SAR38 zeolites outperformed the catalysts comprising HZSM-5 SAR 30 andHZSM-5 SAR 80 zeolites. The catalyst comprising HBeta SAR 150 zeoliteoutperformed the HZSM-5 SAR 30 and HZSM-5 SAR 80 zeolites after 20 hTOS. In addition, the catalyst containing a combination of 80% HBeta SAR25 zeolite and 20% HZSM-5 SAR 80 zeolite also outperformed the catalystcomprising HZSM-5 SAR 80 zeolite alone.

The catalyst comprising HBeta SAR 25 was the best catalyst for thereaction of 4-EP with toluene, with over 81% conversion and over 69%product selectivity to the desired phenol and ethyltoluene products. Thecatalyst comprising HBeta SAR 38 had the highest productivity tophenol+cresols at 1180 g/kg cat/hr and to phenol+cresols+alkylbenzenes(BEX and ethyltoluenes) at 3056 g/kg cat/hr.

The HBeta SAR 25 containing catalyst had only a 2% drop in conversionover 30 h TOS, demonstrating the stability of the catalyst.

Another desirable pathway (disproportionation of toluene) convertstoluene to benzene, ethylbenzene and xylenes (BEX). The catalystcomprising HBeta SAR 25 had a 12.6% product selectivity for convertingtoluene to BEX.

A catalyst comprising a mixture of 80% HBeta SAR 25 with 20% HZSM-5 SAR80 had a slightly lower conversion of about 77% compared to 81% for acatalyst comprising all HBeta SAR 25; however, the selectivity to thedesired products (phenol+ethyltoluene) was improved from 69% to over72%, while the amount of other products was decreased from 10.0% to7.7%.

Example 2

Several commercial zeolites were evaluated for the transalkylation of2,6 xylenol with toluene to form phenol, cresols, benzene, xylenes alongwith other alkylbenzenes. The reaction conditions included using anisothermal fixed bed reactor set to a temperature of 400° C., a pressureof 1350 psig, a WHSV of 2.3 h⁻¹, 1.25 g catalyst, toluene: feed of 10mol/mol, and N₂ feed rate of 25 mL/min. The catalyst was pretreated inN₂ and heated to 200° C. (3° C./min) and held at 200° C. for 2 hfollowed by heating to 450° C. (5° C./min) and held for 3 h beforecooling down to 400° C.

Conversion and selectivity were obtained at 35 h TOS.

As shown in Table 3 and FIG. 2 , the HBeta SAR 25 and HBeta SAR 150zeolites outperformed the HZSM-5 SAR 80 zeolite.

HBeta SAR 150 was the best catalyst for this reaction as well, with over95% conversion and over 55% selectivity to the desired cresols andxylenes products as shown in Table 2. The HBeta SAR 150 had the highestproductivity to phenol+cresols at 931 g/kg cat/hr and tophenol+cresols+alkylbenzenes at 2791 g/kg cat/hr. Furthermore, there wasonly 1% drop in conversion over 25 h TOS. HBeta SAR 25 also performednearly as well as HBeta SAR 150, with over 95% conversion and 52%selectivity to the desired cresols and xylenes products.

Although the 2,6-xylenol conversion was higher compared to 4-EP, themethyl group of the 2,6-xylenol was found to be harder to remove thanthe ethyl group of 4-EP. 4-EP transalkylation only showed 5.4%selectivity to isomerization products (other ethylphenols), while thexylenol transalkylation had a much higher selectivity to isomerizationproducts (other xylenols) of 23.8% for HBeta SAR 25.

Example 3

Commercial zeolites were evaluated for the transalkylation of4-ethylphenol (4-EP) with toluene to form phenol and ethyltoluenes. Theconditions were the same as Example 1 except the gas feed was a mixtureof N₂ at a feed rate of 12.5 mL/min and H₂ at a feed rate of 12.5mL/min.

Conversion and selectivity were obtained at 30 h TOS.

As shown in Table 4 and FIG. 3 , the addition of the H₂ co-feedincreased the ethylphenol conversion of the HZSM-5 SAR 80 to 78.8%compared to 77.9% for the HBeta SAR 25. The phenol and cresolproductivity was also higher at 1050 g/kg cat/hr, but thephenol+cresol+alkylbenzenes productivity of 2349 g/kg cat/hr was lowerthan for HBeta SAR 25 at 2387 g/kg cat/hr.

Example 4

Several commercial zeolites were evaluated for the transalkylation ofcresylic acid (SASOL, CA68) with toluene to form phenol, cresols,ethyltoluene, xylenes, along with benzene and other alkylbenzenes. Thecresylic acid composition was 25 wt % cresols, 34.5 wt % xylenols, 38.5wt % ethylphenols, and 2.0 wt % other compounds (as measured). Thereaction conditions included using an isothermal fixed bed reactor setto a temperature of 400° C., a pressure of 1350 psig, a WHSV of 2.3 h⁻¹,1.25 g catalyst, toluene: cresylic acid of 8.2 g/g, N₂ feed rate of 12.5mL/min, and H₂ feed rate of 12.5 mL/min. The catalyst was pretreated inN₂, heated to 200° C. (3° C./min), and held at 200° C. for 2 h, followedby heating to 450° C. (5° C./min) and holding for 3 h before coolingdown to 400° C.

The conversion and selectivity were obtained at 30 h TOS except for HYSAR which were obtained at 25 h TOS. Negative selectivity means thatcresols were destroyed in the process.

As shown in Table 5 and FIGS. 4A and 4B, HBeta SAR 25 was found to begood at converting both ethylphenol and xylenol in the cresylic acidcompared to the other zeolites tested. HZSM-5 SAR 30 was found to be abetter catalyst for ethylphenol conversion than HBeta SAR 25, with 79%conversion compared to 69% conversion for HBeta SAR 25. However, forxylenol conversion, HBeta SAR 25 was the better catalyst, with 49%conversion, compared with 26% conversion for HZSM-5 SAR 30. HZSM-5 SAR30 was found to have the highest phenol+cresol productivity at 472 g/kgcat/hr slightly higher than HBeta SAR 25 at 468 g/kg cat/hr. However,HBeta SAR 25 had the highest productivity tophenol+cresols+alkylbenzenes at 1235 g/kg cat/hr.

All of the catalysts had greater than 90% selectivity to desiredproducts (phenol, cresols, ethyltoluenes, and BEX) with less than 10%selectivity to other products (diethylphenols, gases, and unknownliquids).

HBeta SAR 25 (80%) was then mixed with several other catalysts (20%) andthe results are shown in FIGS. 5A and 5B. The addition of 20% HZSM-5 SAR30 increased the ethylphenol conversion to 81%, while the xylenolconversion was slightly lower than the pure HBeta SAR 25 at 45.5%conversion. The amount of unknown liquids was also decreased to 3.0%,compared to 5.3% on the pure HBeta SAR 25. This catalyst mixture wasalso found to have the highest phenol+cresol productivity at 509 g/kgcat/hr and phenol+cresols+alkylbenzenes productivity at 1368 g/kgcat/hr.

TABLE 1 IZA Pore Ring Pore Zeolite Code Diameter size Structure Y FAU7.4 × 7.4 12 3D Beta BEA 6.6 × 6.7 12 3D 5.6 × 5.6 12 Mordenite MOR 6.5× 7.0 12 1D 3.4 × 4.8 8 2.6 × 5.7 8 ZSM-5 MFI 5.3 × 5.6 10 3D 5.1 × 5.510 Ferrierite FER 4.2 × 5.4 10 2D 3.5 × 4.8 8

TABLE 2 4EP Ethyl Methyl Conv. Phenol toluenes BEX phenols Catalyst (%)(%) (%) (%) (%) HZSM-5 53.5 33.5 28.8 3.8 1.6 SAR 30 HZSM-5 57.4 36.031.5 4.6 0.5 SAR 80 HBeta 81.0 34.4 34.5 12.6 3.1 SAR 25 HBeta 78.6 31.332.6 15.9 4.3 SAR 38 HBeta 66.5 28.0 28.2 16.9 1.7 SAR 150 HY 31.0 39.720.2 3.6 0.7 SAR 5.2 HMOR 30.0 29.6 18.4 7.2 0.0 SAR 38 80% 76.9 36.835.6 10.1 1.8 HBeta SAR 25 + 20% HZSM-5 SAR 80 Other Phenol + EthylPhenol + Cresols + phenols Others Cresols Alkylbenzenes Catalyst (%) (%)(g/kg cat/h) (g/kg cat/h) HZSM-5 25.5 6.8 495 1073 SAR 30 HZSM-5 22.74.7 591 1308 SAR 80 HBeta 5.4 10.0 968 2439 SAR 25 HBeta 5.3 10.7 11803056 SAR 38 HBeta 11.4 13.8 618 1712 SAR 150 HY 11.4 24.4 365 631 SAR5.2 HMOR 31.9 12.9 216 433 SAR 38 80% 8.0 7.7 969 2354 HBeta SAR 25 +20% HZSM-5 SAR 80

TABLE 3 2, 6 Xyl Other Conv. Phenol Cresols Xylenols Benzene Catalyst(%) (%) (%) (%) (%) HZSM-5 46.2 4.0 2.1 72.3 8.0 SAR 80 HBeta 95.4 5.719.1 23.8 9.7 SAR 25 HY 70.7 2.5 13.9 57.3 5 SAR 5.2 HBeta 95.0 4.0 19.719.3 13.6 SAR 150 HMOR 70.8 0.0 8.1 82.2 1.2 SAR 38 Other Phenol + AlkylPhenol + Cresols + Xylenes benzenes Others Cresols Alkyl benzenesCatalyst (%) (%) (%) (g/kg cat/h) (g/kg cat/h) HZSM-5 7.1 3.4 3.2 66 262SAR 80 HBeta 33.0 1.0 7.7 825 2212 SAR 25 HY 10.7 0.0 10.7 297 558 SAR5.2 HBeta 36.2 1.0 6.3 931 2791 SAR 150 HMOR 4.6 0.0 3.8 131 218 SAR 38

TABLE 4 Other Phenol + 4EP Ethyl Methyl Ethyl Phenol + Cresols + Conv.Phenol toluenes BEX phenols phenols Others Cresols AlkylbenzenesCatalyst (%) (%) (%) (%) (%) (%) (%) (g/kg cat/h) (g/kg cat/h) HZSM-578.8 39.8 37.8 3.7 7.1 9.6 2.0 1050 2349 SAR 80 HBeta 77.9 35.7 34.811.1 4.5 7.1 7.8 1019 2387 SAR 25

TABLE 5 Phenol + EP Xyl. Phenol + Cresols + Conv. Conv. Phenol CresolsEthyltoluenes BEX Others Cresols Alkylbenzenes Catalyst (%) (%) (%) (%)(%) (%) (%) (g/kg cat/h) (g/kg cat/h) HZSM-5 79.0 26.0 42.9 2.0 39.213.5 2.4 472 1138 SAR 30 HZSM-5 42.7 10.0 45.6 −1.0 37.8 15.6 1.9 249611 SAR 80 HZSM-5 6.1 4.5 44.5 19.4 28.4 7.1 0.6 164 273 SAR 280 HBeta69.3 49.1 33.3 5.1 22.7 33.6 5.3 468 1235 SAR 25) HMOR 38.2 25.6 37.8−1.1 23.4 33.5 6.4 169 463 SAR 38 HY 44.7 44.2 36.6 −3.7 22.3 34.5 10.6224 668 SAR 12 80% HBeta 81.0 45.5 34.0 4.9 28.2 29.9 3.0 509 1368 SAR25 + 20% HZSM-5 SAR 30 80% HBeta 71.9 43.4 35.0 4.2 26.6 30.9 3.3 4211123 SAR 25 + 20% HZSM-5 SAR 80 80% HBeta 65.0 46.0 31.5 7.1 20.8 33.76.9 495 1265 SAR 25 + 20% HY SAR 12

As used herein, the term “zone” can refer to an area including one ormore equipment items and/or one or more sub-zones. Equipment items caninclude one or more reactors or reactor vessels, heaters, exchangers,pipes, pumps, compressors, and controllers. Additionally, an equipmentitem, such as a reactor, dryer, or vessel, can further include one ormore zones or sub-zones.

As used herein, the term “about,” means within 10% of the value, orwithin 5%, or within 1%.

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention. It being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims.

1. A process for transalkylation comprising: transalkylating acoal-derived liquid stream comprising alkylphenols in a transalkylationreaction zone under transalkylation conditions in the presence of aco-reactant and a transalkylation catalyst comprising a threedimensional 12 membered ring zeolite with a combination of small andlarge pores to produce a transalkylation effluent stream comprising oneor more of phenol, cresols, and alkylbenzenes, the process havingincreased conversion of alkylphenols to phenol, cresols, andalkylbenzenes compared to a catalyst consisting of HZSM-5 zeolite. 2.The process according to claim 1 wherein the zeolite comprises about 50wt % HBeta or more.
 3. The process according to claim 1 wherein thesilica/metal oxide molar ratio of the zeolite is 80 or below.
 4. Theprocess of claim 1 wherein the transalkylation catalyst furthercomprises about 40 wt % HZSM-5 zeolite or less.
 5. The process of claim1 wherein the transalkylation catalyst comprises about 50% or more HBetazeolite and 1 to 40% HZSM-5 zeolite, and wherein the process hasincreased productivity to phenol or cresols or both compared to atransalkylation catalyst consisting of HZSM-5 zeolite.
 6. The processaccording claim 1 wherein aluminum in a framework structure of thezeolite is substituted by at least one of Fe, Ga, B, Ti, Sn, Zr, andcombinations thereof.
 7. The process of claim 1 wherein the zeolitefurther comprises a promoter comprising one or more of: transitionmetals, alkali metals, alkaline earth metals and rare earth metals,metal oxides, metal sulfides, metal nitrides, metal phosphides, andcombinations thereof.
 8. The process of claim 1 wherein the catalystfurther comprises a support comprising alumina, silica, zirconia,titania, or combinations thereof.
 9. The process of claim 1 wherein thecoal-derived liquid stream comprises a mixture of alkylphenolscomprising two or more of a methylphenol, an ethylphenol, adimethylphenol, a butylphenol, a methylethylphenol, an indanol, and anaphthol, and optionally further comprising a propylphenol.
 10. Theprocess of claim 1 wherein the co-reactant comprises benzene, toluene,or a combination thereof.
 11. The process of claim 1 whereintransalkylating the coal-derived liquid stream takes place in thepresence of hydrogen, nitrogen, or a combination thereof.
 12. Theprocess of claim 1 wherein the transalkylation reaction zone comprises afixed bed reactor, a moving bed reactor, an ebullated bed reactor, afluidized bed reactor, a continuous catalyst regeneration (CCR) reactor,a semi-regenerative reactor, a batch reactor, a continuous stirred tank(CSTR) reactor, a slurry reactor, or combinations thereof.
 13. Theprocess of claim 1 wherein selectivity to phenol, cresols andalkylbenzenes is about 70% or more.
 14. The process of claim 1 whereinthe coal-derived liquid stream comprises a portion of a coal-derivedfeed stream comprising a low temperature coal tar stream, a mediumtemperature coal tar stream, a high temperature coal tar stream, acresylic acid stream, or a crude phenolic mixture.
 15. The process ofclaim 1 further comprising: separating the transalkylation effluent intoa phenol product stream comprising the phenol and an alkylbenzene streamcomprising the alkylbenzenes.
 16. The process of claim 15 furthercomprising: separating the alkylbenzene stream into at least a recycleco-reactant stream comprising one or more of benzene or toluene; andrecycling the recycle co-reactant stream to the transalkylation zone andwherein the recycle co-reactant stream comprises at least a part of theco-reactant.
 17. The process of claim 16 wherein separating thealkylbenzene stream into at least the recycle co-reactant streamcomprises separating the alkylbenzene stream into at least the recycleco-reactant stream and a mixed xylenes stream comprising para-xylene,ortho-xylene, and meta-xylene; and recovering one or more ofpara-xylene, ortho-xylene, or meta-xylene from the mixed xylenes stream.18. The process of claim 15 wherein separating the transalkylationeffluent into the phenol product stream and the alkylbenzene streamcomprises separating the transalkylation effluent into the phenolproduct stream, the alkylbenzene stream, and a cresol product streamcomprising the cresols, and further comprising: recovering the cresolproduct stream.
 19. The process of claim 1 wherein the transalkylationeffluent stream further comprises unreacted alkylphenols, and whereinseparating the transalkylation effluent into the product stream and thealkylbenzene stream comprises separating the transalkylation effluentinto the phenol product stream, the alkylbenzene stream, and anunreacted alkylphenol stream comprising the unreacted alkylphenols, andfurther comprising: recycling the unreacted alkylphenol stream to thetransalkylation reaction zone.
 20. The process of claim 1 furthercomprising: providing a coal-derived feed stream comprising phenol andthe coal-derived liquid stream; separating the coal-derived feed streaminto at least a phenol stream comprising phenol and the coal-derivedliquid stream before transalkylating the coal-derived liquid stream; andrecovering the phenol stream.
 21. The process of claim 1 furthercomprising: providing a coal-derived feed stream comprising phenol andthe coal-derived liquid stream; separating the coal-derived feed streaminto at least a phenol-cresol stream comprising phenol and cresols andthe coal-derived liquid stream before transalkylating the coal-derivedliquid stream; and recovering the phenol-cresol stream.